Technical note

Increasing the filtration rate of phospho-gypsum using surfactant

E.A. Abdel-Aal
a,

, M.M.H. Mahmoud
a
, H. El-Shall
b
, A.K. Ismail
a
a
Central Metallurgical R&D Institute, P.O. Box 87 Helwan, Cairo, Egypt
b
Department of Materials Science and Engineering, Particle Engineering Research Center,
University of Florida, Gainesville 32611, FL. USA
Received 27 January 2006; received in revised form 7 August 2006; accepted 7 August 2006
Available online 18 September 2006
Abstract
Phospho-gypsum is a by-product of processing phosphate rock for phosphoric acid production by acidulation with sulfuric acid.
The size distribution of phosphor-gypsum is a major factor for the economics of the process as it greatly affects the filterability of
the acid. Surface active agents proved to be very effective additive for growth of gypsum crystals. Two phosphate concentrates, one
from Egypt (New Valley) and the other from USA (South Florida) were tested for phosphoric acid production with modification of
gypsum crystals using non-ionic surfactant (CMR-100) containing a mixture of C
6
C
22
sorbitan esters. The studies were carried
out using a semi-continuous laboratory-scale unit simulating the dihydrate process conditions.
The mean diameter of the phospho-gypsum crystals increases in the presence of surfactant for both phosphate concentrates. The
surfactant leads to decreasing the viscosity and modification of gypsum crystals through decreasing the fine size fractions and
attainment of large and uniform crystal shape. The mean diameter of New Valley phosphor-gypsum increases from about 30.0 m
to 36.6 m while the mean diameter of South Florida phospho-gypsum increases from about 30.3 m to about 38.4 m. On the
other hand, the average surface area of both New Valley and South Florida phosphor-gypsum were decreased from 4461 and
8069 cm
2
/g without surfactant to 3284 and 3995 cm
2
/g with surfactant, respectively. In addition, the surfactant leads to an increase
in P
2
O
5
recovery of 12%, which consequently improves plant productivity.
2006 Elsevier B.V. All rights reserved.
Keywords: Solid liquid separation; Filtration; Dihydrate process; Phospho-gypsum; Sorbitan ester surfactant; Crystal growth modifier
1. Introduction
Phosphoric acid is an important intermediate product
for production of fertilizers. It is mainly produced by the
dihydrate process in which phosphate concentrate [fluor-
apatite Ca
10
F
2
(PO
4
)
6
] is leached with sulfuric (H
2
SO
4
)
and weak phosphoric acids to produce phosphoric acid.
A simple diydrate process flow sheet is given in Fig. 1.
Crystallization of calcium sulfate dihydrate (phospho-
gypsum) occurs as leaching is taking place. The primary
reaction for the dihydrate process is as follows (Becker,
1989):
Ca
10
F
2
PO
4

6
14H
3
PO
4
10CaH
2
PO
4

2
2HF
CaH
2
PO
4

2
H
2
SO
4
2H
2
O2H
3
PO
4
CaSO
4
2H
2
O
Ca
10
F
2
PO
4

6
10H
2
SO
4
20H
2
O6H
3
PO
4
10CaSO
4
2H
2
O 2HF
Although the reaction time is fast (2 to 10 min), the
retention time is very long and extends from 2 to 8 h
(Becker, 1989). After leaching, the slurry is filtered and
Hydrometallurgy 85 (2007) 5358
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doi:10.1016/j.hydromet.2006.08.004
counter-current washed to separate the acid from the
phospho-gypsum cake.
The basic objective of phosphoric acid manufacture is
to obtain the highest concentration of phosphoric acid
possible with the maximum yield (Becker, 1989; Slack,
1968). The yield is dependent on the completeness of the
reaction of phosphate concentrate with sulfuric acid, the
efficiency of separation of phosphoric acid from calcium
sulfate and the quantity of wash water required to remove
essentially all the P
2
O
5
fromthe calciumsulfate during the
filtration (Becker, 1989; Slack, 1968). Consequently, the
characteristics of calcium sulfate crystals formed during
the reaction are the most important fundamental factors in
both phosphoric acid filtration rate and the economics of
phosphoric acid production. Using the same filter area, the
production capacity with lower operation (running) costs
can be achieved if the filtration rate is increased.
It is known that the filtration rate depends on
characteristics of filter cake such as crystal size, size
distribution and morphology of the crystals. In other
words, large, spherical and narrow size distribution
crystals give a better filtration rate (Becker, 1989; Slack,
1968). The temperature of the reaction mass and the
phosphoric acid concentration are the controlling factors
governing the degree of hydration of calcium sulfate in
phosphoric acid (Becker, 1989; Slack, 1968).
Many materials are tested as crystal modifiers for
crystallization of calciumsulfate dihydrate e.g., aluminum
sulfate, clay and calcined clay (Abdel-Aal, 1989), alumi-
numhydroxide, pearlite, active silica, active charcoal, and
manganese dioxide (Ismail, 1997; Abdel-Aal et al., 2002),
polymers (Amjad and Hooley, 1986; Kerr et al., 1991;
Zhu, 1996), surfactants (El-Shall et al., 1999, 2000a;
Mahmoud et al., 2004), phosphonates (El-Shall et al.,
2002; Tardos and Mayes, 1997), foreign ions (Rashad
et al., 2004; De Vreugd et al., 1994), carboxylic acids
(Tardos and Mayes, 1997; Badens et al., 1999; Rashad
et al., 2005), and other organic additives such as EDTA
and gelatin (Liu and Nancollas, 1973). To our knowledge,
limited data are reported about the testingof surfactants for
phosphoric acid production on industrial-scale (El-Shall et
al., 2000b). Different surfactant addition methods are
described (El-Shall et al., 2000b) as follows: addition of
surfactant before nucleation; addition of surfactant during
nucleation and addition of surfactant after nucleation.
The present paper summarizes the results of phospho-
ric acid production from Egyptian New Valley phosphate
concentrate and South Florida phosphate concentrate with
addition of non-ionic surfactant aiming at increasing the
filtration rate by 25%and more. Understanding the effects
of the applied surfactant on filtration rates and crystal size
distributions of formed phospho-gypsum crystals is an-
other main objective.
2. Experimental
2.1. Materials characterization
The phosphate concentrates samples used in the
study are from New Valley (Egypt) and from South
Table 1
Chemical analysis of phosphate concentrates (on dry basis)
Constituent, % New Valley (Egypt) South Florida (USA)
P
2
O
5
30.09 27.22
CaO 44.40 42.79
F 2.81 N.D.
SiO
2
2.29 N.D.
Fe
2
O
3
3.80 1.56
Al
2
O
3
0.46 0.95
MgO 0.90 1.58
SO
3
1.50 N.D.
Na
2
O 0.28 0.73
K
2
O 0.04 0.12
Moisture 1.86 N.D.
Insolubles N.D. 8.05
N.D.: Not determined.
Fig. 1. Simple dihydrate process flow sheet.
54 E.A. Abdel-Aal et al. / Hydrometallurgy 85 (2007) 5358
Florida (USA). Chemical analyses of these samples are
given in Table 1. As seen in Table 1 the phosphate
concentrate from New Valley contains extremely high
Fe
2
O
3
content which in turn leads to production of
phosphoric acid of high viscosity and consequently low
filtration rate. The upper merchant-grade limit of Fe
2
O
3
content in phosphate concentrate is correlated with
Al
2
O
3
and P
2
O
5
contents as in the following ratio
(Becker, 1989):
Fe
2
O
3
Al
2
O
3
=P
2
O
5
0:080:1
On the other hand, South Florida phosphate concen-
trate contains high MgO content (1.58%). High MgO
contents increase the acid viscosity and consequently
decrease the filtration rate. The accepted industrially
limit in commercial phosphate concentrates is less than
1.0% MgO.
New Valley and South Florida phosphate concen-
trates contain 80% and 52% 100 mesh as well as 40%
and 30% 200 mesh particle size, respectively. These
sieve analyses are within the typical size suitable for the
dihydrate process.
Pure (95.5%) sulfuric acid of 1.835 g/ml specific
gravity is used for the digestion. The recycle (return) acid
(1820% P
2
O
5
) is accumulated while carrying out the
tests. It is adjusted to the required P
2
O
5
content before
recycling. The surfactant used is a non-ionic Crystal
Modifier Reagent (CMR-100) containing a mixture of
C
6
C
22
Sorbitan Esters provided by University of
Florida, USA. Coulter Laser Diffraction Analyzer
model LS 230 was used for determination of size distri-
bution of the phospho-gypsum crystals produced. JEOL
Scanning Electron Microscope model JSM-6400 was
used for investigation of crystal morphology.
2.2. Apparatus and procedure
The reaction was carried out in cylindrical 1 L reactor
of 10 cm diameter. It was fitted with teflon-coated stirrer
and placed in water bath adjusted at 80 C. The impeller
tip speed was adjusted at 1.44 m/s (550 rpm). The
phosphate concentrate was fed using vibrating rock
feeder. Also, the sulfuric acid was pumped using a
peristaltic pump with Viton tubing. The surfactant/water
suspension was added using small graduated separating
funnel at a dosage of 1.5 kg CMR-100 surfactant per
1 ton P
2
O
5
produced. All the above feeding was done on
continuous bases. Filtration was performed using
Buchner type filter of 4.6 in. diameter. Polypropylene
filter cloth of 80 mesh aperture size was used. Avacuum
pump was used for filtration.
Detailed experimental procedure including reaction
and filtration techniques, and determination of crystal
size distribution as well as calculation of filtration rate,
reaction efficiency, P
2
O
5
recovery and washing effi-
ciency are described elsewhere (El-Shall et al., 1999,
2000a; Mahmoud et al., 2004).
2.3. Calculation of reaction efficiency, P
2
O
5
recovery
and washing efficiency
Reaction efficiency (digestion or process efficiency, %
of extraction or conversion) is defined as the % of P
2
O
5
removed from the phosphate concentrate into solution,
because some of the P
2
O
5
is lost with incompletely
washed gypsum. The reaction efficiency is calculated
according to the following equation (Moudgil, submitted
for publication):
Reaction efficiency 10094*AB*C=D*E
where:
A: % total P
2
O
5
in gypsum cake; B: % water-soluble
P
2
O
5
in gypsum cake; C: % CaO in phosphate
concentrate used to make the acid; D: % P
2
O
5
in
phosphate concentrate used to make the acid; E: % CaO
in gypsum cake.
Also, P
2
O
5
recovery (overall or plant efficiency, or
P
2
O
5
yield) is defined as the % of P
2
O
5
passing from the
phosphate concentrate into the produced phosphoric
acid. It is calculated as follows:
P
2
O
5
recovery 10094*A*C=D*E
The main objective of the washing operation is to
extract, with wash liquor, as much as possible of the
phosphoric acid held by the capillary forces in the
interstices of the gypsum cake. Wash liquor displaces
the impregnating phosphoric acid. The washing
Table 2
Filtration and reaction data of New Valley and South Florida
Item Without surfactant With surfactant
New
Valley
South
Florida
New
Valley
South
Florida
Filtration rate, ton
P
2
O
5
/m
2
day
3.50.3 5.10.3 5.20.6 6.40.4
Moisture % 34.5 28.3 37.9 27.8
Increase in filtration rate, % +48 +25
Reaction efficiency, % 95.3 95.8 96.8 98.6
P
2
O
5
recovery, % 93.2 95.0 95.4 96.4
Washing efficiency, % 97.8 99.2 98.6 97.9
Phosphate concentrates with and without surfactant.
55 E.A. Abdel-Aal et al. / Hydrometallurgy 85 (2007) 5358
(filtration) efficiency is defined as the % of water-
soluble P
2
O
5
passing from the slurry into the produced
phosphoric acid. It is calculated applying the following
relation:
Washing efficiency 10094*B*C=D*E
3. Results and discussion
Abdel-Aal et al. (2004) investigated processing of
South Florida phosphate under different free sulfate
contents ranging from 1.5% to 3.5%. They showed that
the optimum free sulfate content is 2.5% which gave the
highest filtration rate with the highest mean diameter of
the produced gypsum crystals. Ismail (1997) showed
that the optimum free sulfate content for New Valley
phosphate is about 2.0%0.4% which gave the highest
filtration rate. The surfactant type and dose are
phosphate dependent (Becker, 1989).
3.1. Effect of phospho-gypsum size distribution on
processing parameters
Tests at optimum free sulfate content (about 2.0%
0.4%) are carried out using New Valley and South
Florida phosphate concentrates with and without
addition of the surfactant. The amount of applied
surfactant corresponds to 1.5 kg/ton P
2
O
5
produced.
The obtained filtration and reaction data are given in
Table 2. With addition of the surfactant, the filtration
rates are increased by 48% and 25% with New Valley
and South Florida phosphate concentrates, respectively.
This is related to the formation of narrow size
distribution phospho-gypsum crystals with low volume
% of fines as confirmed by the size distribution of
phospho-gypsum crystals given in Fig. 2A, B. It is clear
that the volume percentage of fine phospho-gypsum
crystals (b10 m) is decreased with surfactant addition
from 26% to 18% for New Valley phosphate and
from 22% to 10% for South Florida phosphate.
Also, the volume percentage of fine phospho-gypsum
crystals b400 mesh (b38 m) is decreased with
surfactant addition from 73% to 67% for New
Valley phosphate and from 67% to 50% for South
Florida phosphate. Also, the mean diameter of crystal
size increases with addition of the surfactant. The
statistics of phospho-gypsum crystal size distribution
data show that the mean diameters of New Valley and
South Florida crystals without surfactant are 30.0 m
and 30.3 m, respectively, increasing to 36.6 m and
38.4 m with surfactant. Also, the average specific
surface areas without surfactant are 4461 cm
2
/g and
8069 cm
2
/g, decreasing to 3284 cm
2
/g and 3995 cm
2
/g
Table 3
Statistics of phospho-gypsum crystal size distribution
Item Phospho-gypsum
crystal size
distribution, m
*d
x
d
10
d
50
d
90
New Valley without surfactant 3.7 20.5 71.9 30.0 4461
South Florida without surfactant 2.4 26.5 63.2 30.3 8069
New Valley with surfactant 5.1 26.3 80.9 36.6 3284
South Florida with surfactant 9.4 38.1 62.3 38.4 3995
*d
x
: diameter of crystals passing x% by volume.
Fig. 2. Comparative size distribution of New Valley (A) and South Florida (B) phospho-gypsum crystals (after El-Shall et al., 2000a).
56 E.A. Abdel-Aal et al. / Hydrometallurgy 85 (2007) 5358
with addition of the surfactant, respectively (Table 3). It
is clear that the specific surface area is significantly
reduced for South Florida phospho-gypsum with
surfactant due to agglomeration and forming large
clusters. This is confirmed using SEM. There is
difference in filtration rate with the two phosphate
samples due to differences in phosphate nature (Becker,
1989).
The obtained reaction efficiencies and P
2
O
5
recover-
ies in the presence and absence of surfactant are given in
Table 2. It is clear that, both reaction efficiency and P
2
O
5
recovery are higher with the addition of the surfactant.
This is attributed to the decrease of lattice P
2
O
5
and un-
reacted P
2
O
5
losses. The increase in reaction efficiencies
are 1.5% and 2.8%; and the increase in P
2
O
5
recoveries
are 2.2% and 1.4% with New Valley and South Florida
phosphate concentrates, respectively. The obtained
washing efficiencies are within the industrial limits
from 97% to 99% (Becker, 1989).
3.2. Investigation of phospho-gypsum morphology
One of the most important factors affecting filtration
rate is gypsum morphology. For the best filtration rates,
large crystals of uniform sizes are most desirable. In this
study, the aspect ratio of phospho-gypsum crystals from
New Valley phosphate concentrate is increased as seen in
SEM photomicrographs, Plate 1. In addition, the South
Florida phospho-gypsum crystal shape is clearly changed
from individual tabular crystals to clusters by addition of
the surfactant. This change in morphology could be the
reason for change in size distribution and, consequently,
the enhancement in filtration rates. Fundamentally, these
large clusters are composed of many small crystals. This
may be due to adsorption of surfactants on crystal surfaces
causing hydrophobic (attraction) interactions. Using pure
chemicals and under industrially simulated conditions, it
is found that surfactant increases the aspect ratio of the
formed crystals, decreases the induction time, decreases
Plate 1. SEMphotomicrograph of New Valley phosphogypsum (A and B) with 500 magnification and South Florida phospho-gypsum (C and D) with
200 magnification (after El-Shall et al., 2000a).
57 E.A. Abdel-Aal et al. / Hydrometallurgy 85 (2007) 5358
the nucleation rate, increases surface energy and decreases
the percentage of fine crystals (El-Shall et al., 2005).
4. Conclusion
The effect of the CMR-100 sorbitan ester surfactant on
phospho-gypsum filtration rate and size distribution has
been investigated and compared on two phosphate
concentrates with an addition dose of 1.5 kg CMR-100
surfactant per 1 ton P
2
O
5
produced. The results indicate
that 48%and 25%increase in filtration rate were achieved
with New Valley and South Florida phosphate concen-
trates, respectively. The observed improvements are
attributed to changes in crystal size distribution. By
obtaining narrower size distributions with higher mean
diameters of the crystals sizes, the filtration rates are
highly increased. In addition, a noticeable increase in
reaction efficiencies and P
2
O
5
recoveries are obtained.
The increase in reaction efficiencies are significant as it
ranges between 1.5 and 2.9% and the increase in P
2
O
5
recovery is 1.42.2% depending on the phosphate
concentrate.
Acknowledgements
The Particle Engineering Research Center (PERC) at
the University of Florida is acknowledged for carrying
out particle size distribution analyses. Also, the authors
want to thank New Valley Phosphate Project (Egypt)
and IMC-Agrico Co. (USA) for providing the phosphate
concentrates samples used in this study.
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